CN103408713A - Preparation method and application of supramolecular liquid crystal shape memory polyurethane - Google Patents
Preparation method and application of supramolecular liquid crystal shape memory polyurethane Download PDFInfo
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- CN103408713A CN103408713A CN2013102794222A CN201310279422A CN103408713A CN 103408713 A CN103408713 A CN 103408713A CN 2013102794222 A CN2013102794222 A CN 2013102794222A CN 201310279422 A CN201310279422 A CN 201310279422A CN 103408713 A CN103408713 A CN 103408713A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 107
- 239000004814 polyurethane Substances 0.000 title claims abstract description 58
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 alkoxy benzoic acid Chemical compound 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000007669 thermal treatment Methods 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- FURWKBACCNQCII-UHFFFAOYSA-N NC1=C(C(=O)O)C=CC=C1.CCCCCCCCCCCCCCCC Chemical compound NC1=C(C(=O)O)C=CC=C1.CCCCCCCCCCCCCCCC FURWKBACCNQCII-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000009941 weaving Methods 0.000 claims description 4
- WMOGXURFUQQPPT-UHFFFAOYSA-N NC1=C(C(=O)O)C=CC=C1.CCCCCCCC Chemical compound NC1=C(C(=O)O)C=CC=C1.CCCCCCCC WMOGXURFUQQPPT-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- ZEZJPIDPVXJEME-UHFFFAOYSA-N 2,4-Dihydroxypyridine Chemical compound OC=1C=CNC(=O)C=1 ZEZJPIDPVXJEME-UHFFFAOYSA-N 0.000 claims description 2
- GTRHHOMIEMLBPC-UHFFFAOYSA-N 2-dodecoxybenzoic acid Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1C(O)=O GTRHHOMIEMLBPC-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- SCURALPITAOSRM-UHFFFAOYSA-N C1(=CC=CC=C1)C(=O)O.C(CCCCCCCCCCCCC)ONC1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C(=O)O.C(CCCCCCCCCCCCC)ONC1=CC=CC=C1 SCURALPITAOSRM-UHFFFAOYSA-N 0.000 claims description 2
- HTJWOUWYZPEZND-UHFFFAOYSA-N C1(=CC=CC=C1)O.C(CCCCCCCCCCCCC)ONC1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)O.C(CCCCCCCCCCCCC)ONC1=CC=CC=C1 HTJWOUWYZPEZND-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- PNNXBWWSFIVKQW-UHFFFAOYSA-N [O].CCCCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCCCC PNNXBWWSFIVKQW-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims description 2
- GGOZGYRTNQBSSA-UHFFFAOYSA-N pyridine-2,3-diol Chemical compound OC1=CC=CN=C1O GGOZGYRTNQBSSA-UHFFFAOYSA-N 0.000 claims description 2
- RISYVLILTAVNNP-UHFFFAOYSA-N 2-dodecoxyphenol Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1O RISYVLILTAVNNP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005711 Benzoic acid Substances 0.000 abstract description 2
- 235000010233 benzoic acid Nutrition 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 125000004076 pyridyl group Chemical group 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- KMKBEESNZAPKMP-UHFFFAOYSA-N Biphenylindanone a Chemical compound CC=1C(C)=C2C(=O)C(C3CCCC3)CC2=CC=1OCC(C=1)=CC=CC=1C1=CC=C(C(O)=O)C=C1 KMKBEESNZAPKMP-UHFFFAOYSA-N 0.000 description 12
- 229920006264 polyurethane film Polymers 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000003446 memory effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- MIZWKGYFFWJSGO-UHFFFAOYSA-N ethyl carbamate;pyridine Chemical compound CCOC(N)=O.C1=CC=NC=C1 MIZWKGYFFWJSGO-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 229920000431 shape-memory polymer Polymers 0.000 description 4
- 238000002076 thermal analysis method Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- 230000002457 bidirectional effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- WGFVXVLLUHTNOI-UHFFFAOYSA-N C(CCCCCCCCCCC)OC1=C(C=CC=C1)O.C(CCCCCCCCCCC)OC1=C(C=CC=C1)C(=O)O Chemical compound C(CCCCCCCCCCC)OC1=C(C=CC=C1)O.C(CCCCCCCCCCC)OC1=C(C=CC=C1)C(=O)O WGFVXVLLUHTNOI-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of intelligent materials, and provides a preparation method of supramolecular liquid crystal shape memory polyurethane, which comprises the following steps: reacting pyridyl-containing dibasic alcohol and diisocyanate in an organic solvent at 70-90 DEG C for 1-4 hours, and adding short-chain dibasic alcohol to carry out chain extension reaction to obtain pyridine-containing polyurethane; mixing the pyridine-containing polyurethane with alkoxy benzoic acid or alkoxy phenol to obtain supramolecular liquid crystal polyurethane; and carrying out heat treatment on the pyridine-containing polyurethane at 140-180 DEG C for 5-30 minutes, and cooling to room temperature, thereby obtaining the supramolecular liquid crystal shape memory polyurethane, wherein the number of carbon atoms in the short-chain dibasic alcohol is 2-6. The invention also provides application of the supramolecular liquid crystal shape memory polyurethane prepared by the preparation method in intelligent control systems, optical devices, display units, electronic devices, textiles, toys and daily supplies.
Description
Technical field
The invention belongs to the intelligent material technical field, be specifically related to a kind of preparation method and application of supramolecular liquid crystal shape memory polyurethane.
Background technology
Shape-memory polymer refers to that polymkeric substance passes through ambient conditions, can be out of shape and fixedly obtain interim deformation; And, after the variation of induction external environment, can change again shape and get back to original shape.The characteristics such as compare with other materials, it is light that polymer shape memory material has quality, and distortion easily, easy to process, and adjustable temperature range is wide.Therefore, shape-memory polymer is widely used in weaving, medical treatment, aerospace, the fields such as engineering.At present, except developing various thermic responses, electricity causes response, the shape memory responsivenesss such as wet sensitive sense, the investigator has also continually developed the dual-shaped memory effect, the polymer network of triple shape memory effect (CN102202865A), and the shape-memory polymer of bidirectional shape memory effect (CN10156302A).Therefore, at present the investigator is just improving constantly the responsiveness of polymkeric substance and functional.Thereby improve its application prospect in every respect.
Liquid crystalline polymers is the functional high molecule material that a class has wide application prospect.At present, liquid crystalline polymers or elastomerics have been developed and have had Shape Memory Effect or bidirectional shape memory effect.But, liquid crystalline polymers/elastomerics complicated process of preparation, cost is high, and large-scale production also has certain gap.Yet, as important new function material-supramolecular liquid crystal polymkeric substance, have the supramolecule of utilization reactive force, as hydrogen bond, ionic linkage, coordinate bonds etc. are stabilized in liquid crystal unit on polymkeric substance and form stabilizing liquid crystal supramolecular structure ability.With liquid crystal elastic body, compare, the preparation method of supramolecular liquid crystal polymkeric substance is easy, and cost is low, and efficiency is high, and easily large-scale production, be with a wide range of applications.But, at present, also there is no research report or the patent application about the supramolecular liquid crystal shape-memory polymer both at home and abroad.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect of prior art, and a kind of preparation method and application of supramolecular liquid crystal shape memory polyurethane are provided.
The present invention is achieved in that a kind of preparation method of supramolecular liquid crystal shape memory polyurethane, and it comprises the steps:
The dibasic alcohol that will contain pyridine groups and vulcabond in organic solvent 70~90 ℃ react 1~4h, then add the short chain dibasic alcohol to carry out chain extending reaction, must contain the urethane of pyridine;
The described urethane that contains pyridine is mixed with alkoxybenzoic acid or alkoxy phenol, obtain supramolecular liquid crystal urethane;
Described supramolecular liquid crystal urethane, at 140~180 ℃ of thermal treatment 5~30min, is cooled to room temperature, obtains described supramolecular liquid crystal shape memory polyurethane.
Wherein, in described short chain dibasic alcohol, the number of carbon atom is 2~6.
And, the prepared application of supramolecular liquid crystal shape memory polyurethane in intelligent control system, optics, demonstration equipment, electron device, weaving, toy and articles for daily use of preparation method of above-mentioned supramolecular liquid crystal shape memory polyurethane is provided.
The prepared supramolecular liquid crystal shape memory polyurethane of the preparation method of supramolecular liquid crystal shape memory polyurethane provided by the invention has liquid crystal characteristic and shape-memory properties.The liquid crystal characteristic of described supramolecular liquid crystal shape memory polyurethane shows as in the temperature elevation process, can show the smectic liquid crystal characteristic, or the nematic liquid crystal characteristic.The shape memory characteristic of described supramolecular liquid crystal shape memory polyurethane shows as more than temperature is elevated to glass transition temp, or liquid crystal phase transition temperature is when above, described supramolecular liquid crystal shape memory polyurethane can deform under external force, when temperature under constant External Force Acting, be down to glass transition temp when following, deflection can be fixed more than 80%.More than again being warmed up to glass transition temp, or liquid crystal phase transition temperature is when above, and fixing interim deformation energy one step of urethane is replied, or a minute multistep is returned to original state.In addition, the preparation method of supramolecular liquid crystal shape memory polyurethane provided by the invention compares with other liquid crystalline polymerss, and cost is low, and the preparation method is easy, and liquid crystal changes easily to be regulated; Shape-memory properties easily regulates and controls.
The accompanying drawing explanation
Fig. 1 is the structural representation of the supramolecular liquid crystal shape memory polyurethane for preparing of the preparation method of the supramolecular liquid crystal shape memory polyurethane of the embodiment of the present invention;
Fig. 2 is the thermal analysis curve of the prepared supramolecular liquid crystal urethane secondary temperature elevation at the different heat treatment temperature of the embodiment of the present invention 1;
Fig. 3 is the dynamic properties curve of the prepared supramolecular liquid crystal urethane of the embodiment of the present invention 1;
Fig. 4 is the polarizing microscope picture of the prepared supramolecular liquid crystal urethane of the embodiment of the present invention 1 under 120 ℃;
Fig. 5 is the triple recovery of shape conditional curves of the prepared supramolecular liquid crystal urethane of the embodiment of the present invention 1;
Fig. 6 is the multiple recovery of shape conditional curve of the prepared supramolecular liquid crystal urethane of the embodiment of the present invention 1;
Fig. 7 is the schematic arrangement of the prepared supramolecular liquid crystal urethane of the embodiment of the present invention 2;
Fig. 8 is the polarizing microscope picture of the prepared supramolecular liquid crystal urethane of the embodiment of the present invention 2 under 110 ℃;
Fig. 9 is the polarizing microscope picture of the prepared supramolecular liquid crystal urethane of the embodiment of the present invention 3 under 25 ℃;
Figure 10 is the thermal analysis curve of the prepared supramolecular liquid crystal urethane secondary temperature elevation at the different heat treatment temperature of the embodiment of the present invention 3.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of preparation method of supramolecular liquid crystal shape memory polyurethane, and it comprises the steps:
S01: the dibasic alcohol (HO-Py-OH) that will contain pyridine groups and vulcabond (OCN-R-NCO) in organic solvent 70~90 ℃ react 1~4h, then add the short chain dibasic alcohol (HO-R ' '-OH) carry out chain extending reaction, must contain the urethane (Py-PU) of pyridine;
S02: the described urethane (Py-PU) that contains pyridine is mixed with alkoxybenzoic acid or alkoxy phenol, obtain supramolecular liquid crystal urethane;
S03: described supramolecular liquid crystal urethane, at 140~180 ℃ of thermal treatment 5~30min, is cooled to room temperature, obtains described supramolecular liquid crystal shape memory polyurethane.
Particularly, in step S01, in isocyanic ester in described vulcabond ([NCO]) and the described dibasic alcohol that contains pyridine groups and short chain dibasic alcohol, the mol ratio ([NCO]/[OH]) of hydroxyl ([OH]) sum is 1.0~1.3; In described short chain dibasic alcohol, the number of carbon atom is 1~6; Wherein, the described mass percent that contains the dibasic alcohol of pyridine groups is 30%~50%, and the mass percent of described vulcabond and described dibasic alcohol and be 70%~50%.
The described dibasic alcohol that contains pyridine groups is N, N-dihydroxy ethyl isonicotine, 2,3-dihydroxy-pyridine, 2,4-dihydroxy-pyridine, 2, at least a in the 6-dihydroxy-pyridine; Vulcabond is hexamethylene diisocyanate, 4,4'-methylene-bis (phenylcarbimide), isophorone diisocyanate, 2,6-tolylene diisocyanate, PPDI at least a; Described short chain dibasic alcohol is ethylene glycol, BDO, 1,3-PD, 1, at least a in 6-hexylene glycol, glycol ether.Described organic solvent is tetrahydrofuran (THF), at least a in N,N-dimethylacetamide, DMF, pyridine, formic acid, acetic acid.
In step S02, in described supramolecular liquid crystal shape memory polyurethane, the liquid-crystalization of pyridine urethane can be that solution mixing system is standby, also can the melting mixing preparation.Described alkoxybenzoic acid or alkoxy phenol are long-chain alkoxy yl benzoic acid or long-chain alkoxy base phenol, and the carbonatoms in described alkoxyl group is 8~16, and described alkoxybenzoic acid or alkoxy phenol and the mol ratio that contains the urethane of pyridine are 0.1~1.0.Described alkoxybenzoic acid or alkoxy phenol are octane aminobenzoic acid (hot alkoxy phenol), dodecyloxy phenylformic acid (dodecyloxy phenol), tetradecyloxyaniline phenylformic acid (tetradecyloxyaniline phenol), at least a in n-Hexadecane aminobenzoic acid (n-Hexadecane oxygen base phenol).
In step S03, by described supramolecular liquid crystal urethane, be in order to remove original unstable hydrogen bond at 140~180 ℃ of thermal treatment 5~30min, make to form the hydrogen bond action of more pyridine-carboxyls or hydroxyl, form stable supramolecular liquid crystal thereby make more liquid crystal units access polyurethane backbone by hydrogen bond action.Simultaneously, also be conducive to form the phase separation structure of polyurethane chain, construct supramolecular structure as shown in Figure 1.
The preparation method of the supramolecular liquid crystal shape memory polyurethane that the embodiment of the present invention provides, its basic ideas are first to prepare a kind of urethane that contains the proton acceptor that can form the supramolecule hydrogen bond, then will contain the liquid crystal unit of the proton donor that can form the supramolecule hydrogen bond by after appropriate heat treatment, with non covalent bond form access urethane, form supermolecule liquid crystal structure after the formation hydrogen bond action.Supramolecular liquid crystal shape memory polyurethane prepared by the preparation method of described supramolecular liquid crystal shape memory polyurethane not only has stable liquid crystal characteristic, have wide temperature range smectic liquid crystal phase or Nematic liquid crystalline phase; And have the function of shape memory preferably, and its shape fixed rate is greater than 80%, and the recovery of shape rate is greater than 80%, also has multistep and replys, and the multiple shape memory effect, be with a wide range of applications.
The embodiment of the present invention also provides the application of the prepared supramolecular liquid crystal shape memory polyurethane of the preparation method of above-mentioned supramolecular liquid crystal shape memory polyurethane in intelligent control system, optics, demonstration equipment, electron device, weaving, toy and articles for daily use.
Below by specific embodiment, illustrate the preparation of above-mentioned supramolecular liquid crystal shape memory polyurethane.
Embodiment mono-:
In there-necked flask, add 10.0g N, N-dihydroxy ethyl isonicotine (BINA) raw material, adopt N,N-dimethylacetamide (DMF) as dissolution with solvents BINA, add subsequently liquefaction 4, the 4'-diphenylmethanediisocyanate, increase the temperature to 80 ℃ of reactions 2 hours; Then slowly drip BDO (BDO) and carried out chain extending reaction 2 hours to solution, prepare massfraction 10wt%, the polyurethane solution that contains pyridine of BINA content 40wt%.
By liquid crystal unit and BINA mol ratio, be 0.4(r=0.4), be that the 100g strength of solution is 10wt%, in the above-mentioned urethane that contains pyridine that contains BINA40wt%, add 2.71g(0.0076mol) n-Hexadecane aminobenzoic acid (HOBA), in DMF solution, the machinery powerful mixing is even, obtain the homogeneous composite solution, obtain the solution of supramolecular liquid crystal urethane.
Then, by the solution of described supramolecular liquid crystal urethane, pour mask, 100 ℃ of oven dryings 48 hours, then vacuum-drying 24 hours, obtain dry supramolecular liquid crystal polyurethane film material.
The supramolecular liquid crystal polyurethane film material of described drying, under nitrogen protection, is heated up 160 ℃, and thermal treatment 30 minutes, then, be cooled to room temperature, obtains the supramolecular liquid crystal shape memory polyurethane.The structural representation of described supramolecular liquid crystal shape memory polyurethane as shown in Figure 1.Fig. 2 is the thermal analysis curve of prepared supramolecular liquid crystal urethane secondary temperature elevation at the different heat treatment temperature.Fig. 3 is its dynamic properties curve.Fig. 4 is its polarizing microscope picture under 120 ℃.Fig. 5 is its triple recovery of shape conditional curves.Fig. 6 is its multiple recovery of shape conditional curve.
Embodiment bis-:
In there-necked flask, add 10.0g N, N-dihydroxy ethyl isonicotine (BINA) raw material, adopt N,N-dimethylacetamide (DMF) as dissolution with solvents BINA, adds subsequently isophorone diisocyanate, 80 ℃ of reactions of rising temperature 2 hours; Then slowly drip ethylene glycol (EDO) and carried out chain extending reaction 2 hours to solution, prepare massfraction 10wt%, the polyurethane solution that contains pyridine of BINA content 40wt%.
Subsequently, by liquid crystal unit and BINA mol ratio, be 0.6(r=0.6), be that the 100g strength of solution is 10wt%, add 3.42g(0.0114mol above-mentioned the containing in pyridine urethane that contains BINA40wt%) dodecyloxy phenylformic acid (DOBA), in N,N-DIMETHYLACETAMIDE (DMF) solution, the machinery powerful mixing is even, obtains the homogeneous composite solution, obtains the solution of supramolecular liquid crystal urethane.
Then, by the solution of described supramolecular liquid crystal urethane, pour mask, 100 ℃ of oven dryings 48 hours, then vacuum-drying 24 hours, obtain dry supramolecular liquid crystal polyurethane film material.
Further, the supramolecular liquid crystal polyurethane film material of described drying, under nitrogen protection, heats up 150 ℃, and thermal treatment 20 minutes, then, be cooled to room temperature, obtains the supramolecular liquid crystal polyurethane film material of described drying.The schematic arrangement of described supramolecular liquid crystal shape memory polyurethane as shown in Figure 7.Fig. 8 is its polarizing microscope picture under 110 ℃; Figure 10 is the thermal analysis curve of prepared supramolecular liquid crystal urethane secondary temperature elevation at the different heat treatment temperature.
Embodiment tri-:
In there-necked flask, add 10.0g N, N-dihydroxy ethyl isonicotine (BINA) raw material, adopt N,N-dimethylacetamide (DMF) as dissolution with solvents BINA, add subsequently hexamethylene diisocyanate, adding dibutyl tin dilaurate is catalyzer, 80 ℃ of reactions of rising temperature 2 hours; Then slowly add Resorcinol and carried out chain extending reaction 2 hours to solution, prepare massfraction 10wt%, the polyurethane solution that contains pyridine of BINA content 40wt%.
Subsequently, by liquid crystal unit and BINA mol ratio, be 0.6(r=0.6), be that the 100g strength of solution is 10wt%, add 4.058g(0.0114mol above-mentioned the containing in pyridine urethane that contains BINA40wt%) n-Hexadecane aminobenzoic acid (HOBA), in tetrahydrofuran (THF) (THF) solution, the machinery powerful mixing is even, obtains the homogeneous composite solution, obtains the solution of supramolecular liquid crystal urethane.
Then, by the solution of described supramolecular liquid crystal urethane, pour mask, 100 ℃ of oven dryings 48 hours, then vacuum-drying 24 hours, obtain dry supramolecular liquid crystal polyurethane film material.
The supramolecular liquid crystal polyurethane film material of described drying, under nitrogen protection, is heated up 140 ℃, and thermal treatment 30 minutes, then, be cooled to room temperature, obtains the supramolecular liquid crystal polyurethane film material of described drying.Fig. 9 is its polarizing microscope picture under 25 ℃.
Embodiment tetra-:
In there-necked flask, add 10.0g2,6-dihydroxy-pyridine (HMP) raw material, adopt N,N-dimethylacetamide (DMF) as dissolution with solvents HMP, adds subsequently hexamethylene diisocyanate, adds catalyzer, 80 ℃ of reactions of rising temperature 2 hours; Then slowly add 1,3-PD and carried out chain extending reaction 2 hours to solution, prepare massfraction 10wt%, the polyurethane solution that contains pyridine of HMP content 35wt%.
Subsequently, by liquid crystal unit and HMP mol ratio, be 0.4(r=0.4), be that the 100g strength of solution is 10wt%, add 4.49g(0.0126mol above-mentioned the containing in pyridine urethane that contains HMP35wt%) n-Hexadecane aminobenzoic acid (HOBA), in DMF solution, the machinery powerful mixing is even, obtains the homogeneous composite solution, obtains the solution of supramolecular liquid crystal urethane.
Then, by the solution of described supramolecular liquid crystal urethane, pour mask, 100 ℃ of oven dryings 48 hours, then vacuum-drying 24 hours, obtain dry supramolecular liquid crystal polyurethane film material.
Further, the supramolecular liquid crystal polyurethane film material of described drying, under nitrogen protection, heats up 160 ℃, and thermal treatment 10 minutes, then, be cooled to room temperature, obtains the supramolecular liquid crystal shape memory polyurethane.
Embodiment five:
In there-necked flask, add 10.0g2,4-dihydroxy-pyridine (HOP) raw material, adopt N,N-dimethylacetamide (DMF) as dissolution with solvents HOP, adds subsequently isophorone diisocyanate, adds catalyzer, 80 ℃ of reactions of rising temperature 2 hours; Then slowly add 1,6-hexylene glycol and carried out chain extending reaction 2 hours to solution, prepare massfraction 10wt%, the polyurethane solution that contains pyridine of HOP content 30wt%.
Subsequently, by liquid crystal unit and HOP mol ratio, be 0.8(r=0.8), be that the 100g strength of solution is 10wt%, add 5.27g(0.0216mol above-mentioned the containing in pyridine urethane that contains HOP30wt%) octane aminobenzoic acid (HOBA), in pyridine solution, the machinery powerful mixing is even, obtains the homogeneous composite solution, obtains the solution of supramolecular liquid crystal urethane.
Then, by the solution of described supramolecular liquid crystal urethane, pour mask, lyophilize 48 hours, then 50 ℃ of vacuum-drying 24 hours, obtain dry supramolecular liquid crystal polyurethane film material.
Further, the supramolecular liquid crystal polyurethane film material of described drying, under nitrogen protection, heats up 150 ℃, and thermal treatment 20 minutes, then, be cooled to room temperature, obtains the supramolecular liquid crystal shape memory polyurethane.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the preparation method of a supramolecular liquid crystal shape memory polyurethane, is characterized in that, comprises the steps:
The dibasic alcohol that will contain pyridine groups and vulcabond in organic solvent 70~90 ℃ react 1~4h, then add the short chain dibasic alcohol to carry out chain extending reaction, must contain the urethane of pyridine;
The described urethane that contains pyridine is mixed with alkoxybenzoic acid or alkoxy phenol, obtain supramolecular liquid crystal urethane;
Described supramolecular liquid crystal urethane, at 140~180 ℃ of thermal treatment 5~30min, is cooled to room temperature, obtains described supramolecular liquid crystal shape memory polyurethane.
Wherein, in described short chain dibasic alcohol, the number of carbon atom is 2~6.
2. the preparation method of supramolecular liquid crystal shape memory polyurethane as claimed in claim 1, is characterized in that, in described vulcabond in isocyanic ester and the described dibasic alcohol that contains pyridine groups and short chain dibasic alcohol the mol ratio of total hydroxy be 1.0~1.3.
3. the preparation method of supramolecular liquid crystal shape memory polyurethane as claimed in claim 1, it is characterized in that, wherein, the described mass percent that contains the dibasic alcohol of pyridine groups is 30%~50%, and the mass percent of described vulcabond and described short chain dibasic alcohol and be 70%~50%.
4. the preparation method of supramolecular liquid crystal shape memory polyurethane as claimed in claim 1, is characterized in that, the described dibasic alcohol that contains pyridine groups is N, N-dihydroxy ethyl isonicotine, 2,3-dihydroxy-pyridine, 2,4-dihydroxy-pyridine, 2, at least a in the 6-dihydroxy-pyridine.
5. the preparation method of supramolecular liquid crystal shape memory polyurethane as claimed in claim 1, it is characterized in that, described vulcabond is hexamethylene diisocyanate, 4,4'-methylene-bis (phenylcarbimide), isophorone diisocyanate, 2, at least a in 6-tolylene diisocyanate, PPDI.
6. the preparation method of supramolecular liquid crystal shape memory polyurethane as claimed in claim 1, is characterized in that, described short chain dibasic alcohol is ethylene glycol, BDO, 1,3-PD, 1, at least a in 6-hexylene glycol, glycol ether.
7. the preparation method of supramolecular liquid crystal shape memory polyurethane as claimed in claim 1, is characterized in that, described organic solvent is at least a in tetrahydrofuran (THF), N,N-dimethylacetamide, DMF, pyridine, formic acid, acetic acid.
8. the preparation method of supramolecular liquid crystal shape memory polyurethane as claimed in claim 1, is characterized in that, described alkoxybenzoic acid or alkoxy phenol and the described mol ratio that contains the urethane of pyridine are 0.1~1.0.
9. the preparation method of supramolecular liquid crystal shape memory polyurethane as claimed in claim 1, it is characterized in that, described alkoxybenzoic acid is at least a in octane aminobenzoic acid, dodecyloxy phenylformic acid, tetradecyloxyaniline phenylformic acid, n-Hexadecane aminobenzoic acid, described alkoxy phenol is hot alkoxy phenol, dodecyloxy phenol, tetradecyloxyaniline phenol, at least a in n-Hexadecane oxygen base phenol.
10. as the prepared application of supramolecular liquid crystal shape memory polyurethane in intelligent control system, optics, demonstration equipment, electron device, weaving, toy and articles for daily use of preparation method of supramolecular liquid crystal shape memory polyurethane as described in claim 1~9.
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